jie wang, a dan yuan a and min fang*a,d - royal society ... and characterization of the...

Supplementary Material (ESI) for Journal of Materials Chemistry This journal is (c) The Royal Society of Chemistry 2010

S1

Synthesis and characterization of the interpenetrated MOF-5*

Bi Chen,a Xiujian Wang, b Qianfeng Zhang, c Xiaoyong Xi, a Jingjing Cai, a Huang Qi, a Si

Shi, a Jie Wang,a Dan Yuan a and Min Fang*a,d

Table S1 Attempted synthesis of the non-penetrated MOF-5 using DEF as solvent.

Reactants in g (mmol) or ml (mmol) for DEF

Molar Ratios of Reactants

Reaction Temp.

Method of Removing Entrapped Solvent

Product and Surface Area of Product (m2/g)

1 Zn(NO3)24H2O 3.14 (12.0)

H2BDC 0.665 (4.00)

DEF 100 (890)

1:0.33:74 10524h

a MOF-5-non 33621 (Langmuir) 34002(Langmuir)

Published Work1-2

2 Zn(NO3)26H2O 0.628 (2.11)

H2BDC 0.140 (0.843)

DEFd 20.0 (179)

1:0.40:85

10524h

b. MOF-5-int 1052 (Langmuir) 797 (BET)

Product (71% yield) denoted as B PXRD shown in Figure 1(e) and Figure S1(a)

3 Zn(NO3)26H2O 0.10 (0.34)

H2BDC 0.040 (0.24)

DEF 20.0 (179)

1:0.72:540

10012 h

Heated at 300 C under vacuum.

MOF-5-non with pore volume of 0.95 cm3/g

Published Work3

4 Zn(NO3)26H2O 0.306 (1.03)

H2BDC 0.140 (0.843)

DEFe 20.0 (178)

1:0.82:175 10041 hc

b. MOF-5-int d

Figure S1(b)

a. After exchange with chloroform for 12 h1 or 24 h2, solvent in the products were removed under vacuum at 105C for 12 h1 or 110 C for 16 h.2 b. Product was immerged in dry chloroform for 3 d, chloroform had been changed for 3-4 times in between, and the resulted product was dried at 150 C for 12 h c. By applying a 35 ml, heavy wall, pressure vessel, we observed that the product started to appear after 17 h. d. Identified by XRD power diffraction (Figure S1 in Supporting Information (SI)). d. used as received. e. dried over molecular sieves, the top clear solution was .

a Department of Chemistry, Nanjing Normal University, Nanjing 210097, China. Email: [email protected] b School of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin 541004, China c Department of Applied Chemistry, Anhui University of Technology, Maanshan, Anhui 243002, China d State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, China * Electronic supplementary information (ESI) available: The PXRD patterns of the MOF-5 synthesized using DEF(Figure S1), the MOF-5-int before and after the adsorption measurement, the MOF-5 materials synthesized according to Huangs method at room temperature with and without adding H2O2 solution, the MOF-5-int prepared in a much diluted reactant mixture (1/4 of the original), the packing of the MOF-5-int structure, the N2 adsorption isothermal plot and the pore size distribution.


S2

8 12 16 20 24 28 32 36 40 44 48

b)

a)

Rel

ativ

e In

tens

ity

2-Theta

Figure S1 PXRD patterns of MOF-5-int synthesized using DEF. Synthetic conditions: a) The MOF-5-int material B (No. 2 in Table S1), b) No. 4 in Table S1.

5 10 15 20 25 30 35 40

b)

a)

Rel

ativ

e In

tens

ity

2-Theta

Figure S2. The PXRD patterns of the MOF-5-int material A synthesized using DMF as solvent. a) Product dried at 150 C for 3h ,BET SSA of 724.5 m2/g, Langmuir Surface Area 953.8 m2/g, pore volume (H-K analysis): 0.31 cm3/g, the mean pore width (H-K) method: 5.7 , the intensity ratio of peaks at 6.8, 9.7 and 13.8 = 1 : 0.14 : 1.3; b) Sample (a) after adsorption measurement during which (a) had been activated at 250 C for 20 h, the intensity ratio of peaks at 6.8, 9.7 and 13.8 = 0.25 : 1 : 1.3. (001-807)


S3

5 10 15 20 25 30 35 40 45 50

b)

a)

Rel

ativ

e In

tens

ity

2-Theta

Figure S3. The PXRD patterns of the MOF-5-int material B synthesized using DEF as solvent. a) Product dried at 150 C for 12 h, BET SSA of 797 m2/g, Langmuir Surface Area1052 m2/g, pore volume (H-K analysis): 0.40 cm3/g, the mean pore width (H-K) method: 5.25 the intensity ratio of peaks at 6.8, 9.7 and 13.8 = 1 : 0.14: 0.68; b) Sample (a) after adsorption measurement during which (a) had been activated at 250 C for 6 h, the intensity ratio of peaks at 6.8, 9.7 and 13.8 = 1: 0.40 : 1.1CB-165-2.


S4

5 10 15 20 25 30 35 40

0

20000

40000

60000

80000

100000

120000

140000R

elat

ive

Inte

nsity

2-Theta

Figure S4 The PXRD pattern of the product prepared by a much diluted solution. The molar

ratio of Zn(NO3)2: H2BDC: H2O: DMF =1:0.75:11.0: 665 (about 1/4 of the normal concentration).

(a)


S5

(b)

(c)


S6

(d)

Figure S5. Wireframe diagrams of the MOF-5-int A viewed along a (a), b (b),c (c), other directions (d), showing different types of pores. C is gray, Zn is pink, O is red and H is white.

0.0 0.2 0.4 0.6 0.8 1.00

50

100

150

200

250

300

Qua

ntity

ads

orbe

d(cm

3 /g)

Relative pressure(P/P0)


S7

(a) N2 adsorption/desorption isothermal plot


S8

0.40 0.44 0.48 0.52 0.56 0.60 0.64 0.68 0.72 0.76 0.80 0.84 0.88 0.92 0.96 1.00

0.00

0.04

0.08

0.12

0.16

0.20

0.24

0.28

0.32

0.36

0.40

Cum

ulat

ive

pore

vol

ume

(cm

3 /g)

Pore diameter (nm)

(b) Cumulative pore volume versus pore diameter calculated by H-K method.

4.8-6.84 : 0.26 cm3/g; 6.78-7.00 : 0.013 cm3/g.

(c) Cumulative pore volume versus pore diameter calculated by DFT method


S9

(d) Pore distribution calculated by DFT method

Figure S6. N2 adsorption/desorption results of the MOF-5-int material A001-807

0.0 0.2 0.4 0.6 0.8 1.0

0

50

100

150

200

250

300

Qua

ntity

abs

orbe

d (c

m3 /g

STP

)

Relative pressure (P/P0)



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4 6 8 10

0.00

0.04

0.08

0.12

0.16

0.20

0.24

0.28

0.32

0.36

a)C

umul

ativ

e P

ore

Vol

ume(

cm3 /g

)

Pore Width()

(b) Cumulative pore volume versus pore diameter calculated by H-K method. 4.8-6.64 :

0.278 cm3/g; 6.64-7.04: 0.018 ;


S11

0.0 0.2 0.4 0.6 0.8 1.0

0

50

100

150

200

250

N2 q

uant

ity (c

m3/

g ST

P)

Relative pressure (P/P0)


4 8 12 16 20 24 28 32 36 40 44 48 52

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

Cum

ulat

ive

pore

vol

ume

(cm

3 /g)

Pore diameter ()

(b) Cumulative pore volume versus pore diameter calculated by H-K method. 4.8-8.0 : 0.31

cm3/g; 8.0-16 0.04 cm3/g.

4 6 8 10 12 14 16 18 20

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0.20

0.22

0.24

0.26

Cum

ulat

ive

pore

vol

ume

(cm

3 /g)

Pore diameter ()

(c) Cumulative pore volume versus pore diameter (DFT method). Total: 0.25cm3/g;


S12

Figure S8 N2 adsorption/desorption results of the MOF-5-int material CCB-170.

5 10 15 20 25 30 35 40

b)

a)

Rel

ativ

e In

tens

ity

2-theta

Figure S9. The MOF-5 material synthesized according to Huangs method at room temperature. (a) Without adding any acid(b) adding 3 drops of H2O2 solution (30%).

References 1 S. Hermes, F. Schroder, S. Amirjalayer, R. Schmid, R. A. Fischer, J. Mater. Chem., 2006,

16, 2464. 2 K. Schrock, F. Schroder, M. Heyden, R. A. Fischer, M. Havenith, Phys. Chem. Chem.

Phys., 2008, 10, 4732. 3 J. Gonzalez, R. N. Devi, D. P. Tunstall, P. A. Cox, P. A. Wright, Micropor. Mesopor. Mater,

2005, 84, 97.

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